Bioadhesives and processes for making same

ABSTRACT

A dried distiller soluble based bioadhesive composition and method for producing the dried distiller soluble based bioadhesives are disclosed, as well as derivatives thereof. The produced dried distillers solubles derives from co-products of corn fermentation facilities, and is advantageously comprised in part of water-soluble proteins. The method for producing the dried distillers solubles generally involves separation and/or introduction of targeted constituents and/or physiochemical treatment to facilitate use as an adhesive. Use of the method and bioadhesive compositions disclosed herein will improve the economics of fermentation by increasing co-product value, reducing plant-wide energy utilization, decreasing waste and emissions, and increasing overall product yield from each bushel of corn consumed.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of the U.S.Provisional Patent Application Nos. 61/599,215 filed on Feb. 15, 2012and 61/614,862 filed Mar. 23, 2012, which are fully incorporated hereinby reference.

BACKGROUND

The present disclosure generally relates to the renewable fuel,renewable chemical, polymer, plastic, elastomer, resin and adhesiveproduction industries; and more specifically, to improving theproduction, product mix and economics of fermentation processes, such ascorn to ethanol manufacturing processes and the like. More particularly,the present disclosure relates to bioadhesives formed from drieddistillers solubles produced in the corn fermentation process.

Bioadhesives are natural polymeric materials that act as adhesives.Exemplary bioadhesives are those derived from soy flour. Soy floursuitable for use as bioadhesives was, and still is, generally obtainedby removing some or most of the oil from the soybean, yielding aresidual soy meal that was subsequently ground into extremely fine soyflour. The resulting soy flour was then, generally, denatured (i.e., thesecondary, tertiary and/or quaternary structures of the proteins werealtered to expose additional polar functional groups capable of bonding)with an alkaline agent and, to some extent, hydrolyzed (i.e., thecovalent bonds were broken) to yield adhesives for wood bonding underdry conditions.

The use of soybeans as a bioadhesive has various limitations. First andforemost is that making a bioadhesive from soybeans requires removal ofthe soybean oil. Excessive soybean oil creates weaker bonds and createsissues during heat pressing of the adhesive, wherein a Maillard reactioncan take place resulting in browning or blackening of the material,creating a distinct odor and weakening the overall adhesive value.Moreover, the removal of oil from soybeans typically uses a flammablehexane extraction process.

Soybeans naturally have a relatively high concentration ofcarbohydrates. The high concentration of carbohydrates can createmoisture instability issues. In addition, the high carbohydrate levelsin soy flour require more complex crosslinking techniques andchemistries to improve the water resistance problem of soybeanbioadhesives. The use of soy protein isolates (SPI) have been used,wherein a chemical process is applied to the soy flour to remove starchand/or carbohydrates from the soybean meal. This process createsadditional costs and mostly uses hazardous chemistry and methods.

Soybean protein flour also requires a separate hydrolyzation process tomake the proteins have an adhesive nature. In most prior art, water isadded to the soybean flour along with a caustic or chemical that canraise the pH sufficient to hydrolyze the proteins. Caustic chemicalssuch as sodium hydroxide, potassium hydroxides and other harmfulchemicals are often used. Not only does the hydrolyzation processrequire additional and potentially harmful chemical processing steps, itfurther adds to the cost of such materials.

Because of the many limitations with the use of soybeans for preparingbioadhesives, other materials are now being investigated.

The U.S. ethanol industry is generally based on the fermentation ofcorn. It has grown significantly over the past 30 years, from anindustry-wide output of 175 million gallons per year in 1980 to about13.5 billion gallons in 2011. Demand for ethanol in the United States isexpected to continue to increase due to a number of factors, includingpolicies designed to reduce reliance on fossil fuels, volatile petroleumprices, heightened environmental concerns, and energy independence andnational security concerns. Corn ethanol can thus be expected tocomprise an increasingly larger portion of the U.S. liquid fuel supplyduring the next several years.

The production and use of renewable chemicals has also grownsignificantly in recent years for many of the same reasons, with anattendant increase in demand for renewable raw materials. As a result,there is substantial interest and ongoing research involving developmentof commercial processes for the conversion of corn and its derivativesinto various renewable fuels and chemicals, including substitutes forfossil fuel-derived chemicals and industrial polymers, such as plastics,elastomers, resins, and adhesives.

With its established corn fermentation infrastructure, the U.S. cornethanol industry can be expected to be the most practical pathway toincrease the production and use of such renewable fuels and chemicals onglobally-meaningful scales. To participate in that growth, cornfermentation facilities will need to evolve to achieve improvedproduction efficiencies.

Because of its relatively low investment and operational requirements,dry milling has become the primary method for corn to ethanolproduction. In the dry milling process, corn is first screened andground to a flour. The resulting flour is combined with water and thestarch within the corn is conventionally hydrolyzed into sugar byliquefaction and saccharification. The mixture is then fermented withyeast to convert the sugar into ethanol and carbon dioxide. About 30% ofthe mass of each kernel of corn accepted by corn ethanol producers isconverted into ethanol in this manner. The output of fermentation, amixture of ethanol, water, protein, carbohydrates, fat, minerals, solidsand other unfermented components, is then distilled to boil off ethanolfor recovery, purification and sale, leaving the remainder of themixture in the bottom of the distillation stage.

The remainder in the bottom of the distillation stage is referred to aswhole stillage and is typically subjected to a press or centrifugationprocess to separate the coarse solids from the liquid. The liquidfraction is commonly referred to as distillers solubles or thinstillage. Thin stillage is frequently concentrated in an evaporator tobecome condensed distillers solubles, which is also commonly referred toas thin stillage syrup or thin stillage concentrate. The coarse solids,or wet cake, collected from the centrifuge or press are known as wetdistillers grains. Drying the distillers grains produces drieddistillers grains. The distillers grains can be combined with thecondensed distillers solubles to form what is commonly referred to aswet distillers grains with solubles, which can then be dried to formdried distillers grains with solubles (also referred to as drieddistillers solubles). The dried distillers grains or dried distillersgrains with solubles typically have a moisture content of less than 20%by weight to greater than 3% by weight although greater or lesseramounts of moisture content may be employed as may be desired fordifferent applications.

In some instances, the condensed distillers solubles is subjected to ahigh temperature drying process to form dried distillers solubles, whichreportedly has been used as a thermoplastic additive with metal oxideand fiber in the preparation of extruded articles.

In other instances, partially concentrated thin stillage or condenseddistillers solubles, prior to being combined with the wet distillersgrains, is subjected to a corn oil extraction process to remove at leasta portion of the oil contained therein. The extracted crude corn oil canbe used as a feedstock for the production of biodiesel and otherproducts. The remaining condensed distillers solubles with at least aportion of the oil removed is then typically combined with the wetdistillers grains to form the wet distillers grains with solubles andfurther dried as dried distillers grains with solubles for use as animalfeed. Exemplary corn oil extraction processes are disclosed in U.S. Pat.Nos. 7,601,858, 7,608,729, 8,008,516, and 8,008,517, all of which areincorporated by reference in their entireties.

The non-fermentable byproducts of the corn to ethanol fermentationprocess are currently being investigated for use as bioadhesives. Forexample, U.S. Pat. No. 7,618,660 to Mohanty et al. discloses the use ofurea or caustic treated dried distillers grains with solubles to form abioadhesive for paperboard binding. In Monhanty, distiller dried grainswith solubles are treated with urea and/or a strong base such as sodiumhydroxide to hydrolyze water-insoluble proteins. The resulting solutionis then filtered to at least partially remove inert fiber (cellulose andhemicellulose) and other insoluble materials prior to final dewatering,leaving a complex mixture of low molecular weight compounds with lowviscosity. The high solids and residual inert fiber content of theresulting distiller dried grains with solubles-derived adhesive reducesthe overall percentage of active protein and thus decreasesfunctionality in most resin and adhesive applications.

The usage of currently processed dried distillers grains or drieddistillers grains with solubles is problematic for bioadhesives.Constituent carbohydrates and insoluble components within the grainsmust be processed with hazardous chemicals that require additionalprocess stages, energy, and expensive equipment comprised of alloyshaving high corrosion resistance. Secondary processing to grind thedried distillers grains or dried distillers grains with solubles into afine powder would also be required. Building and operating suchprocesses at the scale would be very expensive and would yield anadhesive with functionality diminished by the presence of highconcentrations of carbohydrates and insoluble materials.

Accordingly, it would be desirable for a more robust renewable materialfor bioadhesives that does not possess these limitations.

BRIEF SUMMARY

Disclosed herein are dried distiller soluble based bioadhesivecompositions and processes for making the same. In one embodiment, abioadhesive composition includes dried distillers solubles, which isderived from thin stillage.

In another embodiment, a method of making a bioadhesive compositioncomprises evaporating at least a portion of water from thin stillageobtained from a corn-to-ethanol fermentation process to form condenseddistillers solubles; drying the condensed distillers solubles to formdried distillers solubles; and forming a bioadhesive composition withthe dried distillers solubles.

In another embodiment, a process for bonding one component to anothercomponent comprises applying a bioadhesive composition to a surface ofat least one of the components, wherein the bioadhesive compositioncomprises dried distillers solubles; and contacting the one componentwith the other component, wherein the bioadhesive composition istherebetween.

The disclosure may be understood more readily by reference to thefollowing detailed description of the various features of the disclosureand the examples included therein.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

Referring now to the figures wherein the like elements are numberedalike:

The FIGURE illustrates a process flow diagram for forming the drieddistillers solubles in accordance with the present disclosure.

DETAILED DESCRIPTION

The present disclosure is generally directed to bioadhesives derivedfrom dried distillers solubles and methods for making the same. Thedried distillers solubles derive exclusively from the wet processingstream of the corn-to-ethanol fermentation process and can be comprisedof water-soluble functionalized proteins, among other constituents. Aswill be discussed in greater detail, the use of dried distillerssolubles in the bioadhesive composition overcomes many of the problemsnoted in the prior art as it relates to bioadhesives in general and asit relates to the prior art's use of dried distillers grains. Moreover,because of the uniqueness of the dried distillers solubles, theproperties can be readily manipulated by the use of additives and/or bycompositional changes as a function of processing and isolating thedried distillers solubles. With regard to compositional changes, becausethe dried distillers solubles is ultimately obtained from whole stillage(i.e., the residue remaining after ethanol distillation), it should beapparent that modification, physical or chemical, of the finalbioadhesive properties can be made to any one of the product streamsupstream from the dried distillers solubles as well as on the drieddistillers solubles itself.

For ease in understanding the present disclosure, it is important todistinguish between dried distillers solubles and dried distillersgrains. As is well known in the art, the left over byproducts of thecorn-to-ethanol fermentation process are referred to as whole stillage,which is generally the non-fermentable grains, byproducts, and waterthat falls to the bottom of the distillation column once the ethanol isdistilled. The whole stillage is typically mechanically treated (e.g.,decanted, centrifuged, pressed, or the like) to produce two fractions: asubstantially solids fraction referred to as wet distillers grains and asubstantially aqueous based fraction referred to as thin stillage. Thedried distillers solubles is derived from the substantially aqueousbased thin stillage fraction and will include a relative high amount ofwater soluble proteins, which provides many unique properties.

The thin stillage can be concentrated by use of evaporators to producecondensed distillers solubles (also referred to as thin stillageconcentrate, or thin stillage syrup), which may be further treated toremove oil entrained therein. The condensed distillers solubles, onceobtained, is oftentimes mixed with the wet distillers grains and furtherdried in a dryer to form dried distillers grains, which may then be usedas animal feed. In some processes, the wet distillers grains may bedried without the addition of the thin stillage concentrate to form adried grain product that is also referred to by those in the art asdried distillers grains, which may still or may not have an appreciablemoisture content depending on the extent of drying.

The composition of the condensed distillers solubles can vary dependingon the processing facility, ethanol process, and corn variety, growingseason and post processing methods. However, on a dry matter weightbasis condensed distillers solubles typically have about equal partsamino acids/proteins to fatty acid materials. One facility reported acomposition of condensed distillers solubles as containing dry matter of33.4% of which the composition included crude protein of 20.8%, crudefat of 22.2%, crude fiber of 2.8%, ADF of 2.3%, NDF of 4.3%, and ash of9.2%.

In the present disclosure, at least a portion of the condenseddistillers solubles is further dried to produce dried distillerssolubles and employed in a bioadhesive composition, as is, modified, orin combination with other components. The dried distillers solubles mayor may not have an appreciable moisture content depending on the extentof drying. Applicants have discovered that bioadhesives derived from thedried distillers solubles provide excellent adhesive properties that canbe readily tailored for a variety of applications without the problemsnoted with the use of dried distillers grains or the expense related tothe use of soybeans.

The dried distillers solubles resultant material by itself is generallyin a compactable powder or granular form and, in some embodiments, canbe used directly as an adhesive, wherein the dried distillers solublesforms an adhesive layer between two components, and by the usage of heatand pressure can be configured to flow and cure to form an adheredproduct. Alternatively, aqueous solutions of the dried distillerssolubles and/or any dried distillers solubles precursor or co-productcan readily be made and applied at a desired viscosity. Still further,the dried distillers solubles based bioadhesive composition may furtherbe compounded with other materials, wet and/or dry, to provide desiredproperties for a given application. The particular adhesive applicationis not intended to be limited. By way of example only, the drieddistillers solubles bioadhesive can be used for its adhesive propertiesin papers, wood veneers, in the production of wood and agrifibercomposite panels such as particleboard, medium density fiber board(MDF), oriented strand board (OSB), laminated lumber products, and thelike.

The resultant dried distillers solubles material can also be used as aresin extender, wherein the dried distillers solubles is blended withanother adhesive such as a soy protein based bioadhesive, for example,to lower its cost and provide various functional advantages in the finalblend. As such, the dried distillers solubles can be an adhesive orresin extender for various resins currently used in the wood compositesand paper industry such as phenol formaldehyde, and other types ofresins.

Referring now to the FIGURE, process 100 illustrates a method forforming dried distillers solubles from the corn-to-ethanol fermentationprocess 110. After aqueous fermentation of the starch within the corn toproduce ethanol, the ethanol 123 is removed in a distillation step 120leaving behind an aqueous mixture of post fermentation byproducts, i.e.,whole stillage (WS) 121. The whole stillage 121 is then separated in aseparation process 130 into two fractions: the wet distillers grains(WDG) 131 and the thin stillage fraction (TS) 132. The thin stillagefeedstream 132 is then subjected to an evaporation process 140 to removemoisture content so as to form condensed distillers solubles (CDS) 141.Typically, the thin stillage 132 is first fed to an evaporator e.g., amultistage evaporator, to remove at least a portion of the watercontained therein, i.e., 1^(st) removal: evaporation. In ethanolproduction facilities, the evaporation temperatures within theevaporator generally are in a range of about 100 to about 230° F., andmore typically, in a range of about 110 to about 200° F. The condenseddistillers with solubles 141 can then be subjected to an oil removalprocess to remove at least a portion of the oil contained therein so asto form defatted condensed distillers solubles 142 (CDS-F). The amountof oil that is removed can be used to modify the properties of thecondensed distillers solubles once dried, i.e., dried distillerssolubles.

Optionally, the condensed distillers solubles 141 and/or the defattedcondensed distillers solubles 142 can be further evaporated in a secondevaporation step to remove additional moisture therein to form a superconcentrated condensed distillers solubles 151, which may also besubject to an oil removal step or in the case of defatted condenseddistillers solubles subjected to an additional oil removal step to formdefatted concentrated distillers solubles. Further concentration and oilremoval may be continued as may be desired.

The amount of oil (fat) removed and the removal method are not intendedto be limited to any particular amount/process so long as at least aportion is removed relative to thin stillage by itself, wherein theamount removed can be used to tailor the adhesive properties. Inaddition to the production of dried distillers solubles 171 and itssubsequent use as a bioadhesive, the extracted corn oil itself can beused for various applications including, but not limited to, productionof biodiesel, thereby transforming what was previously considered as alow value product into a significant revenue stream for ethanol plantoperator.

The condensed distillers solubles 141, concentrated condensed distillerssolubles 151, defatted condensed distillers solubles 142, or defattedconcentrated condensed distillers solubles 152 or like feed streams canbe subject to wet compounding 160, which includes wet mixing thefeedstream with other components, at least one of which may be asolution or water. In this step, additional additives, described in moredetail below, can be incorporated to form a modified distillerssolubles.

The condensed distillers solubles 141, concentrated condensed distillerssolubles 151, defatted condensed distillers solubles 142, and/ordefatted concentrated condensed distillers solubles, as well as thecorresponding wet compounded distillers solubles can then be subjectedto thermal drying at step 170, individually or in various combinations,to further reduce the moisture content therein to an amount suitable forforming the dried distillers solubles 171 for the particular endapplication. The dried distiller solubles 171 which may be used as is ormay be dry compounded with dry ingredients. Again, doing so can be usedto manipulate the final adhesive properties as may be desired fordifferent adhesive applications. For example, the adhesive propertiesfor a given application may desire tacky adhesion, e.g., a post-it note,or may require a more permanent bond, e.g., formation of particle board,or may require a permanent bond that is water insensitive or may be hotmelted. Likewise, bond strength can be varied.

Table 1 provides a general comparison on a dry matter basis of acondensed distillers solubles composition without oil extraction and acondensed distillers solubles composition with at least a portion of theoil removed. Reference to defatted condensed distillers solubles is notintended to infer that oil is completely removed from the drieddistillers with solubles. In some embodiments, it may be beneficial tosubject the condensed distillers solubles to multiple oil [and/or water]extraction steps to further decrease and manipulate the amount of oil[and/or water] contained in the dried distillers with solubles productmaterial. In most embodiments, the oil content in the dried distillerswith solubles product material is from 3 to 15% by weight althoughhigher or lower amounts of oil may be desired in certain applications

TABLE 1 Condensed Partially Defatted Distillers Condensed DistillersSolubles Solubles Protein (%) 18 21 Fat (%) 20 7 Carbohydrates (%) 48 56Ash (%) 14 16 Total (%) 100 100

As demonstrated in Table 1, the amount of oil can easily be varied,which can directly affect the final bioadhesive properties once thecondensed distillers solubles are dried to form the dried distillerssolubles.

In a similar manner, the other constituents defining the drieddistillers solubles composition can be varied. For example, the thinstillage 132 or condensed distillers with solubles 141 can be treated toremove a portion of the carbohydrates and/or a portion of the proteinscontained therein. For example, a portion of the low molecular weightproteins, may be removed. Likewise, non-fermented starch andcarbohydrates can be removed or partially removed to tailor thebioadhesive properties by CO₂ extraction, additional fermentation, orthe like. Still further, upstream treatment may include filtration,membrane filtration or centrifugation technologies to isolate and reduceadditional components such as the suspended solids (dines) or selecteddissolved solids as may be desired for different applications.

Alternatively, the dried distillers with solubles can be treated as isor upstream to modify one or more of the constituents within thecomposition. For example, the proteins and/or carbohydrates can befunctionalized with different materials to provide further manipulationof the bioadhesive properties. By way of example, protein modificationscan include, for example, treating proteins with an acid, base or otheragent that alters the structure of one or more of the amino acid sidechains, which, in turn, alters the character of the protein and/or aminoacids. For example, the high glutamine and asparagine of prolamines,particularly zein from corn, provides a means for manipulating thecharge characteristics of the protein by deamidation, thereby providinga wide range of hydrophobicity. In one embodiment, deamidation involvesmild acid catalyzed deamidation at a pH of about 1 at temperatures fromabout 25° C. to about 65° C. for a period of time sufficient toaccomplish the desired level of deamidation. In some embodiments, acidsthat form stable dispersions and are useful within these classesinclude, without limitation, lactic acid, citric acid, malonic acid,phosphoric acid, fumaric acid, maleic acid, maleic anhydride, maleatedpropylenes, glutaric acid, transaconitic acid, acetic acid, propionicacid, sorbic acid, cysteine and glycyl glycine. In one embodiment,lactic acid in the form of polylactic acid is used. In anotherembodiment, maleated propylenes, such as G-3003 and G-3015 manufacturedby Eastman chemicals are used.

The thin stillage and condensed distillers solubles feedstreams haveconventionally been viewed as low-value by-products, i.e., wasteproducts. Problematically, the chemical and physical characteristics ofcondensed distillers with solubles adversely affect (and dilute thevalue of) wet distillers grains when combined therewith. The resultingproduct stream, the precursor to dried distillers grains with solubles,has reduced protein content and is stickier and less tolerant tospoilage than it would be without addition of condensed distillers withsolubles following evaporation. Consequently, producers have to burnmore fossil fuel-derived natural gas to dry dried distillers grains withsolubles longer than would otherwise be required in order to vaporizemore water and to avoid handling and spoilage issues. Low moisturecontent translates directly into extended storage life. Producers havegenerally had little choice but to follow the standard industry practiceof combining condensed distillers with solubles with wet distillersgrains prior to drying for the want of an economically and technicallyfeasible alternative. An object of this disclosure is to provide such analternative and empower producers to reduce these inefficiencies bydiverting and separately processing condensed distillers with solubles.As a result, the wet distillers grains does not require the extendeddrying times since spoilage as a function of moisture content is less ofa concern.

Thin stillage and its more concentrated form of concentrated distillerssolubles form are generally comprised of water, protein, fat,carbohydrates, ash, and relatively minor amounts of other fermentationbyproducts. At least some of the protein in the feedstream has beenhydrolyzed as a function of the fermentation process conditions and iswater-soluble. The fat is substantially comprised of glycerides and ispresent in a free, bound and/or emulsified state. The carbohydratefraction is further comprised of various sugars, partially-hydrolyzedstarch, and insoluble polysaccharides (cellulose, hemicellulose andlignin). Ash includes residual minerals. Fermentation byproducts includeglycerol, lactic acid, acetic acid, yeast, and the like.

By the time concentrated distillers solubles exits the evaporators, itsprotein and other constituents have changed significantly due tocontinuous treatment during the fermentation process with hot water,enzymes, caustic, acid, urea and/or other chemicals, at times underpressure and/or vacuum, for more than two days. Many of these processconditions are severe and are generally known to facilitate at leastsome degree of hydrolysis, denaturation and other presently favorablereactions and reactants.

By way of example, ethanol facilities using the method taught byWinsness in U.S. patent application Ser. No. 11/908,891 incorporatedherein by reference in its entirety, iteratively wash the whole stillagewith at least a portion of the thin stillage after initial separation ofwhole stillage into wet distillers grains and thin stillage. This stepincreases the content of lower density, low molecular weight and solublecomponents in the thin stillage to enhance derivative co-product value,e.g., dried distiller solubles. Moreover, as disclosed by Winsness, fatremoval efficiencies can be optionally increased by chemical additionand/or by increasing temperature and/or concentrated thin stillage orconcentrated distillers solubles residence time at targetedtemperatures. Using such methods, concentrated distillers solubles mightbe held at an elevated temperature for an extended period of time at apH of, for example, 3.5 to 4.5, before removing at least some fat (oil)and directing the condensed distillers solubles for final evaporation.

The dried distillers solubles is produced by introducing the liquidfeedstream into a drying gas stream and recovering the dried distillerssolubles from the drying gas stream. An exemplary process is a hightemperature pulse combustion process as described in U.S. Pat. No.7,937,850 to Tate et al., incorporated herein by reference in itsentirety. In this process, the condensed distillers solubles areintroduced into the drying gas stream at a temperature of about 600° F.to about 1800° F.

In another embodiment, the dried distillers solubles is obtained using alow temperature process. In this manner, the proteins contained withinthe dried distillers solubles are subjected to a less thermallyaggressive process relative to the preceding pulse combustion processand as a result, less denaturing of the proteins and oxidation of thevarious constituents contained within the feedstream may occur. In thismethod, some or all of the liquid feedstream is conducted to a vessel orvessels for thermal treatment, with or without one or more additive(s)in one or more sequential stages under proscribed conditions and times.The vessel or vessels used in this method can be operated in batch orcontinuous fashion, and can incorporate one or more devices foraccomplishing thermal treatment by convection, conduction and/orradiation, in sequence and/or concurrently.

The low temperature drying process applied can be applied to the liquidfraction, e.g., thin stillage, condensed distillers solubles, defattedcondensed distillers solubles, and the like and generally includes afluidized bed apparatus configured to heat the liquid fraction e.g., CDS(or thin stillage) to a temperature less than 300° F. in mostembodiments, less than 250° F. in other embodiments, and less than 200°F. in still other embodiments. In one embodiment, the drying process isconfigured to provide the DDS in a powder and/or granular form with amoisture content of about 3 to about 20% by weight, and in otherembodiments, about 5 to about 12% by weight. The various additives canbe added by wet mixing prior to the drying process or dry mixing.

In another embodiment, the dried distillers solubles is obtained using alow temperature process. In this manner, the proteins contained withinthe DDS are subjected to a less thermally aggressive process relative tothe preceding pulse combustion process and as a result, less denaturingof the proteins and oxidation of the various constituents containedwithin the feedstream may occur. In this method, some or all of theliquid feedstream is conducted to a vessel or vessels for thermaltreatment, with or without one or more additive(s) in one or moresequential stages under proscribed conditions and times. The vessel orvessels used in this method can be operated in batch or continuousfashion, and can incorporate one or more devices for accomplishingthermal treatment by convection, conduction and/or radiation, insequence and/or concurrently.

In an exemplary mode of this method, the liquid feedstream is conductedthrough one or more nozzles into a manifold at the top of vessel orvessels comprising an initial stage of thermal treatment (“TT1”). A gasor gasses are simultaneously fed into TT1 through one or more inlets, atflow rates and temperatures that are metered to precisely controlintermediate temperature, residence time and other relevant processvariables such that, for example, moisture is removed while avoidingundesirable particle deformation or reactions. In an alternativeembodiment, TT1 may also incorporate use of a fluidized bed (“FB1”) atthe base of the TT1 vessel or vessels, into which a gas or gases are fedat rates and temperatures sufficient to achieve incipient fluidizationand, as desired, to facilitate heat and/or mass transfer, reactionsand/or other relevant process objectives during TT1. The temperaturesand process conditions used in this process can be configured tomaintain the DDS product material during drying at a temperature lessthan 300° F. in most embodiments, less than 250° F. in otherembodiments, and less than 200° F. in still other embodiments.

Another aspect involves further conveyance of the intermediatefeedstream from TT1 into a single or plurality of additional thermaltreatment zones (TT2, TT3 and so on), each incorporating a means ofconvection, conduction and/or radiation to achieve desired processobjectives. In one method, such stage or stages incorporate a fluidizedbed (FB2, FB3 and so on), into which a gas or gases are fed at rates andtemperatures as may be sufficient to, for example, gently heat and/orcool the intermediate at iteratively lower temperatures. Air adjustedweirs can be additionally incorporated into the method to manageresidence times.

Alternatively, the drying apparatus may be configured to supplement theconvective processes with conductive processes, such as by incorporatingan induction heater or intercooler into the base of a fluid bed.Emissive methods can also be incorporated, such as by adding infraredenergy emitters into the housing walls, or by adding a zone in which thefeed material is treated by electromagnetic radiation at wavelengths,intensities and times sufficient to gently heat the interior ofparticles to enable more efficient, lower temperature convection whileavoiding excessive surface dehydration and degradation, or other adversereactions that could impair functionality.

By way of a further example, any of the foregoing thermal treatmentmethods could optionally involve introduction of one or more additives,which may include liquid feedstream or any co-product from a prior orsubsequent stage of this invention or the fermentation facility, duringany stage of thermal treatment to regulate the characteristics asdesired to, for example, prevent degradation or otherwise render theresulting DDS suitable for further processing and/or its anticipated enduse.

The thermal treatment processes described above may also be utilized tofacilitate targeted reactions, such as functionalization,polymerization, crosslinking and the like, as may be necessary tocondition the DDS for its intended end use.

Other thermal treatment method can be used to supplement convectiveprocesses with conductive methods, such as by incorporating an inductionheater or intercooler into the base of a fluid bed. Emissive methods canalso be incorporated, such as by exposing the liquid fraction toinfrared energy emitters, or by adding a zone in which the liquid feedmaterial is treated by electromagnetic radiation at wavelengths,intensities and times sufficient to gently heat the interior ofparticles to enable more efficient, lower temperature convection whileavoiding excessive surface dehydration and degradation, or other adversereactions which could impair functionality.

By way of a further example, any of the foregoing thermal treatmentmethods could optionally involve introduction of one or more additives,which may include liquid feedstream or any co-product from a prior orsubsequent stage of this invention, during any stage of thermaltreatment to regulate the characteristics as desired to, for example,prevent degradation or otherwise render the resulting dried distillerssolubles suitable for further processing and/or its anticipated end use.Any additive can be incorporated in a finishing step of dry compounding.

The drying thermal treatment processes described above may also beutilized to facilitate targeted reactions, such as functionalization,polymerization, crosslinking and the like, as may be necessary tocondition the dried distillers solubles for its intended end use.

The dried distillers solubles and/or derivative or any of the upstreamintermediate product feedstreams including, but not limited to, wholestillage, thin stillage, condensed distillers solubles, defattedcondensed distillers soluble, and the like, can comprise at leastanother component, to manipulate the properties of the bioadhesive suchas, but not limited to, improving and/or controlling the viscosity,adhesive properties, shelf-life, and stability. Non-limiting examples ofadditional components include tackifiers, plasticizers (plasticizingoils or extender oils), waxes, antioxidants, UV stabilizers, colorantsor pigments, fillers, flow aids, biocides, lubricants, water, oil,coupling agents, crosslinking agents, surfactants, catalysts solvents,hydrolyzing agents, and combinations thereof. The foregoing additivescan be incorporated before or after drying thermal treatment.

In some embodiments, the dried distillers solubles and/or derivative orany of the upstream product feedstreams disclosed herein can comprise atackifier or tackifying resin or tackifier resin. The tackifier maymodify the properties of the composition such as viscoelastic properties(e.g., tan delta), rheological properties (e.g., viscosity), tackiness(i.e., ability to stick), pressure sensitivity, and wetting property. Insome embodiments, the tackifier is used to improve the tackiness of thecomposition. In other embodiments, the tackifier is used to reduce theviscosity of the composition. In further embodiments, the tackifier isused to render the composition a pressure-sensitive adhesive. Inparticular embodiments, the tackifier is used to wet out adherentsurfaces and/or improve the adhesion to the adherent surfaces.

Any tackifier known to a person of ordinary skill in the art may be usedand is generally added to the bioadhesive composition as opposed toupstream feedstreams. Tackifiers suitable for the compositions disclosedherein can be solids, semi-solids, or liquids at room temperature.Non-limiting examples of tackifiers include (1) natural and modifiedrosins (e.g., gum rosin, wood rosin, tall oil rosin, distilled rosin,hydrogenated rosin, dimerized rosin, and polymerized rosin); (2)glycerol and pentaerythritol esters of natural and modified rosins(e.g., the glycerol ester of pale, wood rosin, the glycerol ester ofhydrogenated rosin, the glycerol ester of polymerized rosin, thepentaerythritol ester of hydrogenated rosin, and the phenolic-modifiedpentaerythritol ester of rosin); (3) copolymers and terpolymers ofnatured terpenes (e.g., styrene/terpene and alpha methylstyrene/terpene); (4) polyterpene resins and hydrogenated polyterpeneresins; (5) phenolic modified terpene resins and hydrogenatedderivatives thereof (e.g., the resin product resulting from thecondensation, in an acidic medium, of a bicyclic terpene and a phenol);(6) aliphatic or cycloaliphatic hydrocarbon resins and the hydrogenatedderivatives thereof (e.g., resins resulting from the polymerization ofmonomers consisting primarily of olefins and diolefins); (7) aromatichydrocarbon resins and the hydrogenated derivatives thereof; (8)aromatic modified aliphatic or cycloaliphatic hydrocarbon resins and thehydrogenated derivatives thereof; and combinations thereof.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise or incorporate a plasticizer or plasticizing oil or anextender oil that may reduce viscosity and/or improve tack properties.Any plasticizer known to a person of ordinary skill in the art may beused in the adhesion composition disclosed herein. Non-limiting examplesof plasticizers include olefin oligomers, low molecular weightpolyolefins such as liquid polybutene, phthalates, mineral oils such asnaphthenic, paraffinic, or hydrogenated (white) oils (e.g. Kaydol oil),vegetable and animal oil and their derivatives, petroleum derived oils,and combinations thereof. In some embodiments, the plasticizers includepolypropylene, polybutene, hydrogenated polyisoprene, hydrogenatedpolybutadiene, polypiperylene and copolymers of piperylene and isoprene,and the like having average molecular weights between about 350 andabout 10,000. In other embodiments, the plasticizers include glycerylesters of the usual fatty acids and polymerization products thereof.

In some embodiments, a suitable insoluble plasticizer may be selectedfrom the group which includes dipropylene glycol dibenzoate,pentaerythritol tetrabenzoate; polyethylene glycol400-di-2-ethylhexoate; 2-ethylhexyl diphenyl phsophate; butyl benzylphthalate, dibutyl phthalate, dioctyl phthalate, various substitutedcitrates, and glycerates.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise a wax that may reduce the melt viscosity in addition toreducing costs. Any wax known to a person of ordinary skill in the artcan be used in the adhesion composition disclosed herein. Non-limitingexamples of suitable waxes include petroleum waxes, polyolefin waxessuch as low molecular weight polyethylene or polypropylene, syntheticwaxes, paraffin and microcrystalline waxes having melting points fromabout 55 to about 110° C., Fischer-Tropsch waxes and combinationsthereof. In some embodiments, the wax is a low molecular weightpolyethylene homopolymer or interpolymer having a number averagemolecular weight of about 400 to about 6,000 g/mole.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise an antioxidant or a stabilizer. Any antioxidant known to aperson of ordinary skill in the art may be used in the adhesioncomposition disclosed herein. Non-limiting examples of suitableantioxidants include amine-based antioxidants such as alkyldiphenylamines, phenyl-a-naphthylamine, alkyl or aralkyl substitutedphenyl-α-naphthylamine, alkylated p-phenylene diamines,tetramethyl-diaminodiphenylamine and the like; and hindered phenolcompounds such as 2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)benzene;tetrakis (methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane(e.g., IRGANOX™ 1010, from Ciba Geigy, N.Y.);octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX™ 1076,commercially available from Ciba Geigy) and combinations thereof.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise an UV stabilizer that may prevent or reduce the degradationof the compositions by UV radiation. Any UV stabilizer known to a personof ordinary skill in the art may be used in the adhesion compositiondisclosed herein. Non-limiting examples of suitable UV stabilizersinclude benzophenones, benzotriazoles, aryl esters, oxanilides, acrylicesters, formamidine, carbon black, hindered amines, nickel quenchers,hindered amines, phenolic antioxidants, metallic salts, zinc compoundsand combinations thereof.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise a colorant or pigment. Any colorant or pigment known to aperson of ordinary skill in the art may be used in the adhesioncomposition disclosed herein. Non-limiting examples of suitablecolorants or pigments include inorganic pigments such as titaniumdioxide and carbon black, phthalocyanine pigments, and other organicpigments.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise a filler. Any filler known to a person of ordinary skill inthe art may be used in the adhesion composition disclosed herein.Non-limiting examples of suitable fillers include sand, talc, dolomite,calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminumsilicate, alumina, hydrated alumina, glass bead, glass microsphere,ceramic microsphere, thermoplastic microsphere, barite, wood flour,magnesium carbonate, calcium hydroxide, calcium oxide, magnesium oxide,aluminum oxide, silicon oxide, iron oxide, boron nitride, titaniumoxide, talc, pyrophyllite clay, silicate pigment, polishing powder,mica, sericite, bentonite, pearlite, zeolite, fluorite, dolomite, quicklime, slaked lime, kaolin, chlorite, diatomaceous earth, andcombinations thereof.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise a catalyst. Suitable catalysts include without limitation,metallic catalysts and non-metallic catalysts. Metal catalysts include,without limitation, metal oxides, including, for example, zinc oxide,titanium dioxide, copper oxides, (cuprous oxide and/or cupric oxide),aluminum oxide, calcium oxide, stannous oxide, lead oxide and othermetal oxides; and metals, for example, zinc, titanium, copper, iron,nickel, zirconium, and aluminum. Other catalysts include, withoutlimitation, fly ash and Portland cement.

Some oxides also assist with odor reduction and increase the shelf life.Without being bound by theory, oxides, such as titanium dioxide, mayreduce auto-oxidation.

In further embodiments, the dried distillers solubles and/or derivativeor any of the upstream product feedstreams disclosed herein optionallycan comprise a crosslinker. Crosslinking agents also have the ability toincrease the mechanical and physical performance of the presentbioadhesive. As used herein, crosslinking generally refers to linking atleast two polymer chains comprised, for example, of proteins, peptides,polysaccharides, and/or synthetic polymers or the corn protein material.

Suitable crosslinking agents include one or more of metallic salts(e.g., NaCl or rock salt) and salt hydrates (which may improvemechanical properties), urea, formaldehyde, urea-formaldehyde,polyesters, phenol and phenolic resins, melamine, methyl diisocyanide(MDI), polymeric methyl diphenyl diisocyanate (pMDI), polymerichexamethylene diisocyanate (pHMDI), amine-epichlorohydrin adducts,epoxides, zinc sulfate, aldehydes and urea-aldehyde resins epoxides,aldehyde, aldehyde starch, dialdehyde starch, glyoxal, urea glyoxal,urea-aldehyde, polyamine epichlorohydrin resin,polyamidoamine-epichlorohydrin resin, polyalkylenepolyamine-epichlorohydrin, amine polymer-epichlorohydrin resin epoxy,resin mixtures, combinations thereof, and the like. The same or similaragents may also serve as binders.

The amine-epichlorohydrin adducts are defined as those prepared throughthe reaction of epichlorohydrin with amine-functional compounds. Amongthese are polyamidoamine-epichlorohydrin resins (PAE resins),polyalkylenepolyamine-epichlorohydrin (PAPAE resins) and aminepolymer-epichlorohydrin resins (APE resins). The PAE resins includesecondary amine-based azetidinium-functional PAE resins, tertiary aminepolyamide-based epoxide-functional resins and tertiary aminepolyamidourylene-based epoxide-functional PAE resins. It is alsopossible to use low molecular weight amine-epichlorohydrin condensates.

Additional additives can include a fiber additive. Suitable fibersinclude any of a variety of natural and synthetic fibers. Cellulosefibers include, without limitation, those from wood, agriculturalfibers, including flax, hemp, kenaf, wheat, soybean, switchgrass, andgrass, fibers obtained from paper and other fiber recycling, including,without limitation, household and industrial paper recycling streams,fibrous waste from the paper or wood industries, including paper millsludge. Synthetic fibers include fiberglass, Kevlar, carbon fiber,nylon; mixtures or combinations thereof, and the like. Mineral or silicaadditives may also be used. The fiber can modify the performance of thebiopolymers. For example, longer fibers can be added to impart higherflexural and rupture modulus to the cured or dried bioadhesive.

Nanomaterials may also be used as fillers, including NanoCell (LDIComposites), which is a blend of cellulose, minerals and clay that hasbeen processed into a submicron material. It is derived from paper millsludge. NanoCell also contains small percentages of metals and titaniumdioxide. Other forms of nanomaterials, such as nanofibers, nanotubes,nanocellulosics, nanoclays and other forms of nanomaterials may also beincluded in the dried distillers solubles biocomposite additive and/orthe biopolymer.

Other materials that can include components found in latex paint,including, without limitation, latex compounds, including, withoutlimitation, acrylic latexes such as styrenated acrylic latex; calciumcarbonate, colorants, dispersants, such as, for example, napthalenesulfonic acid condensation products; ammonium hydroxide; surfactants;glycol ethers, including (propylene glycol) methyl ether;2,2,4-trimethylpentanediol-1,3-monoisobutyrate; sodium nitrite; ethyleneglycols, such as triethylene glycol bis(2-ethylhexanoate); dryingagents, such as metal oxides, including, without limitation, zirconiumoxides, cobalt oxides and iron oxides, as well as ethylene oxides andethylene oxide derivatives and condensates, including, withoutlimitation, fatty alcohol ethoxylate, alkylphenol ethoxylate, fatty acidethoxylate, ethoxylated fatty amines, and the like; preservatives,emulsifiers and thickeners.

Additional additives include citric acid including citric acidmonohydrate contains many carboxyl groups that are expected to interactwith both proteins and cellulosic based materials at elevatedtemperatures.

The dried distillers solubles can also be dry blended with a wide rangeof additional powder resin as a bioextender to either lower the cost ofthe petrochemical resin powder or provide functional advantages to theoverall adhesive blend. Dried distillers solubles can also be added tovarious formaldehyde resins wherein the proteins can scavenge theresidual formaldehyde and increase the biobased content of the adhesive.Such powder or liquid resins include but not limited to: phenolformaldehyde, urea formaldehyde and melamine formaldehyde adhesives.

The following examples are presented for illustrative purposes only, andare not intended to limit the scope of the invention.

Example 1

In this example, condensed distillers solubles with at least a portionof the oil removed was further evaporated in an evaporator to a moisturecontent of about 50% by weight. The liquid was then placed into afluidized bed spray drier in which the material was recirculated toprovide a granular mixture. The granular mixture was dried to twodifferent moisture contents.

One sample had a moisture percentage of about 12% and the other samplehad a moisture content of 5% by weight The granular material had a verylight bright yellow color and emitted minimal odor. The granularmaterial was sandwiched between a particle board and a wood veneer paneland heat pressed at 300° F. and 10 pounds per square inch (psi). Oncecooled to room temperature, the veneer was qualitatively tested foradhesion by physically attempting to separate the veneer from theparticle board by hand. In this example, the veneer panel could not beseparated from the particle board.

Example 2

In this example, the dried distillers solubles with at least a portionof the oil removed in accordance with Example 1 was blended withglycerine obtained from biodiesel production at a 50% ratio and mixed.The material was used to laminate two kraft papers together using heatand pressure.

Example 3

In this example, the dried distillers solubles with at least a portionof the oil removed in accordance with Example 1 was blended with waterat a 1:1 ratio by weight and mixed. The material was used to laminatetwo particle boards together. The sample was clamped to maintainpressure for about 24 hours. The clamps were removed and physicalseparation of the particle boards by hand was not achieved, therebyindicating good adhesion.

Example 4

In this example, the dried distillers solubles with at least a portionof the oil removed in accordance with Example 1 was blended with waterat a 1:1 ratio by weight and mixed. 5% Lactic Acid was added and mixed.Then 5% magnesium oxide was added and mixed. The material was used tolaminate two particle boards together. The sample was clamped tomaintain pressure for about 24 hours. The clamps were removed andphysical separation of the particle boards by hand was not achieved,thereby indicating good adhesion.

Example 5

In this example, the dried distillers solubles with at least a portionof the oil removed in accordance with Example 1 was blended with waterat a 1:1 ratio by weight and mixed. 5% Ammonium Polyphosphate was addedand mixed. Then 5% magnesium oxide was added and mixed. The material wasused to laminate two particle boards together. The sample was clamped tomaintain pressure for about 24 hours. The clamps were removed andphysical separation of the particle boards by hand was not achieved,thereby indicating good adhesion.

Example 6

In this example, the dried distillers solubles with at least a portionof the oil removed in accordance with Example 1 was blended with waterat a 1:1 ratio by weight and mixed. Separately, a magnesium chloridesolution was made with 25 parts of hydrated magnesium chloride mixedwith 15 parts water and mixed, then 60 parts of magnesium oxide wasadded to create the magnesium chloride solution. 10% of the magnesiumchloride solution was then added with the aqueous solution containingthe dried distillers solubles and mixed. This material was used tolaminate 2 layers of kraft paper together.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to make and use the invention. The patentable scope of the inventionis defined by the claims, and may include other examples that occur tothose skilled in the art. Such other examples are intended to be withinthe scope of the claims if they have structural elements that do notdiffer from the literal language of the claims, or if they includeequivalent structural elements with insubstantial differences from theliteral languages of the claims.

What is claimed is:
 1. A bioadhesive composition comprising drieddistillers solubles.
 2. The bioadhesive composition of claim 1, furthercomprising an additive, wherein the additive is a tackifier selectedfrom the group consisting of natural rosins, modified rosins, copolymersof natural terpenes, polyterpene resins, aliphatic hydrocarbon resins,and combinations thereof.
 3. The bioadhesive composition of claim 1,further comprising an additive, wherein the additive is a plasticizerselected from the group consisting of olefin oligomers, phthalates,mineral oils, vegetal oils, animal oils, and combinations thereof. 4.The bioadhesive composition of claim 1, further comprising an additive,wherein the additive is a crosslinker.
 5. The bioadhesive composition ofclaim 1, further comprising an additive, wherein the additive is a waxselected from the group consisting of petroleum waxes, polyolefin waxes,synthetic waxes, paraffin, microcrystalline waxes, and combinationsthereof.
 6. The bioadhesive composition of claim 1, wherein the drieddistillers solubles comprise modified water soluble proteins.
 7. Thebioadhesive composition of claim 1, further comprising a soy beanprotein isolate.
 8. The bioadhesive composition of claim 1, furthercomprising an additive, wherein the additive is a filler selected fromthe group consisting of sand, talc, clay, silica, mica, magnesium oxide,mica, silicon dioxide, kaolin, iron oxide, and combinations thereof. 9.The bioadhesive composition of claim 1, further comprising an additive,wherein the additive is a fiber selected from cellulose fibers andsynthetic fibers.
 10. A method of making a bioadhesive compositioncomprising: evaporating at least a portion of water from thin stillageobtained from a corn-to-ethanol fermentation process to form condenseddistillers solubles; drying the condensed distillers solubles to formdried distillers solubles; and forming a bioadhesive composition withthe dried distillers solubles.
 11. The method of claim 10, furthercomprising wet compounding the dried distillers solubles with anadditive.
 12. The method of claim 10, further comprising dry compoundingthe dried distillers solubles with an additive.
 13. The method of claim11, wherein the additive comprises a plasticizer, a crosslinker, a wax,a filler material, a soy protein isolate, an antioxidant, a UVstabilizer, a colorant, a flow aid, a biocide, a lubricant, an oil, acoupling agent, a fiber, a tackifier, a metal oxide, a surfactant, acatalyst, a solvent, or a hydrolyzing agent, or mixtures thereof. 14.The method of claim 11, wherein the plasticizer is selected from thegroup consisting of olefin oligomers, phthalates, mineral oils, vegetaloils, animal oils, and combinations thereof.
 15. The method of claim 11,wherein the tackifier is selected from the group consisting of naturalrosins, modified rosins, copolymers of natural terpenes, polyterpeneresins, aliphatic hydrocarbon resins, and combinations thereof.
 16. Themethod of claim 11, wherein the wax is selected from the groupconsisting of petroleum waxes, polyolefin waxes, synthetic waxes,paraffin, microcrystalline waxes, and combinations thereof.
 17. Themethod of claim 11, wherein the filler is selected from the groupconsisting of sand, talc, clay, silica, mica, magnesium oxide, mica,silicon dioxide, kaolin, iron oxide, and combinations thereof.
 18. Themethod of claim 12, wherein the additive comprises a plasticizer, acrosslinker, a wax, a filler material, a soy protein isolate, a fiber, ametal oxide or mixtures thereof.
 19. The method of claim 12, wherein theplasticizer is selected from the group consisting of olefin oligomers,phthalates, mineral oils, vegetal oils, animal oils, and combinationsthereof.
 20. The method of claim 12, wherein the tackifier is selectedfrom the group consisting of natural rosins, modified rosins, copolymersof natural terpenes, polyterpene resins, aliphatic hydrocarbon resins,and combinations thereof.
 21. The method of claim 12, wherein the wax isselected from the group consisting of petroleum waxes, polyolefin waxes,synthetic waxes, paraffin, microcrystalline waxes, and combinationsthereof.
 22. The method of claim 12, wherein the filler is selected fromthe group consisting of sand, talc, clay, silica, mica, magnesium oxide,mica, silicon dioxide, kaolin, iron oxide, and combinations thereof. 23.The method of claim 10, further comprising chemically modifying at leastone of a whole stillage, thin stillage, the condensed distillerssolubles and dried distillers solubles.
 24. The method of claim 10,further comprising removing a selected amount of oil from the condenseddistillers solubles such that the dried distillers solubles contains adesired amount of oil therein.
 25. The method of claim 10, furthercomprising treating the thin stillage or the condensed distillerssolubles with an acid or base.
 26. The method of claim 10, whereindrying comprises convection at an elevated temperature.
 27. The methodof claim 10, wherein drying is a drying gas stream at a temperature ofabout 600° F. to about 1800° F.
 28. The method of claim 10, whereinevaporating the condensed distillers solubles comprises reducing themoisture content to less than about 50% by weight.
 29. A process forbonding one component to another component, the process comprising:applying a bioadhesive composition to a surface of at least one of thecomponents, wherein the bioadhesive composition comprises drieddistillers solubles; and contacting the one component with the othercomponent, wherein the bioadhesive composition is therebetween.
 30. Theprocess of claim 29, wherein the dried distillers solubles is acompactable powder.
 31. The process of claim 29 wherein the compositionfurther comprises a tackifier, a plasticizer, a wax, an antioxidant, aUV stabilizer, a colorant, a filler, a flow aid, a biocide, a lubricant,an oil, a coupling agent, a crosslinking agent, a surfactant, acatalyst, a solvent, or a hydrolyzing agent.